Conversion of Carbon Dioxide to Organic Products

ABSTRACT

The invention relates to various embodiments of an environmentally beneficial method for reducing carbon dioxide. The methods in accordance with the invention include electrochemically or photoelectrochemically reducing the carbon dioxide in a divided electrochemical cell that includes an anode, e.g., an inert metal counterelectrode, in one cell compartment and a metal or p-type semiconductor cathode electrode in another cell compartment that also contains an aqueous solution of an electrolyte and a catalyst of one or more substituted or unsubstituted aromatic amines to produce therein a reduced organic product.

CROSS REFERENCES TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No. 61/206,28 filed on Jan. 29, 2009, which is hereby incorporated by reference.

STATEMENT OF GOVERNMENT SUPPORT

This invention was made with United States government support from Natural Science Foundation Grant No. CHE-0606475 The United States Government has certain rights in this invention.

INTRODUCTION

In recent years, high levels of atmospheric carbon dioxide (CO₂), emitted, for example, from industry, fossil fuel combustion and utilities, have been linked to global climate change. A greenhouse effect attributed to carbon dioxide is indicated as one cause of the warming phenomenon of the earth. Many responsible sources contend that the condition of the earth's atmosphere is such that, to avoid the predicted dire consequences of global warming effects, removal of a portion of the existing, as well as new, quantities of carbon dioxide from the atmosphere is needed.

Various options for carbon dioxide reduction have been proposed. In addition to energy conservation, carbon capture and storage, the process of separating CO₂ from emission sources and transporting it to a storage location for long-term (indefinite) isolation, and carbon sequestration, the process of permanently storing CO₂ underground, have garnered the most attention to date. However, these technologies face significant challenges and are presently far from being cost effective. In addition, sequestration has raised serious environmental concern, legal and regulatory issues due to the unknown ramifications of permanently storing CO₂ underground.

A significant issue with the removal of carbon dioxide from the atmosphere is the very large energy input to overcome the entropic energies associated with isolating and concentrating a diffuse gas. As noted, current strategies for removal of carbon dioxide from the atmosphere are either inefficient, cost prohibitive, or produce toxic by-products such as chlorine. To lower global carbon dioxide levels and reduce new carbon dioxide emissions, it remains critical to develop economically feasible processes to remove vast quantities of carbon dioxide from the atmosphere or gas streams.

BRIEF DESCRIPTION

In accordance with embodiments of the invention, an electrocatalytic system is provided that allows carbon dioxide to be converted at very modest overpotentials to highly reduced species in aqueous solution, in other words, carbon-carbon and/or carbon-hydrogen bonds are formed in aqueous solution under very mild condition utilizing a minimum of energy. In some embodiments, the required energy input may be generated from an alternative energy source or directly using visible light depending on how the system is implemented.

In embodiments of the invention, the reduction of carbon dioxide is suitably catalyzed by aromatic heterocyclic amines, e.g., pyridinium, imidazole and their substituted derivatives. These simple organic compounds have been found to be effective and stable homogenous electrocatalysts and photoelectrocatalysts for the aqueous multiple electron, multiple proton reduction of carbon dioxide to organic products such as formic acid, formaldehyde, and methanol. For production of methanol, the reduction of carbon dioxide proceeds along 6 e⁻ transfer pathway. High faradaic yields for the reduced products have been found in both electrochemical and photoelectrochemical systems at low reaction overpotentials.

It has previously been thought that metal-derived multi-electron transfer was necessary to achieve highly reduced products such as methanol. Surprisingly, the simple aromatic heterocyclic amine molecules in accordance with embodiments of the invention are capable of producing many different chemical species on route to methanol through multiple electron transfers instead of metal-based multi-electron transfer.

The invention thus relates to various embodiments of environmentally beneficial methods for reducing carbon dioxide. The methods in accordance with the invention include electrochemically or photoelectrochemically reducing the carbon dioxide in an aqueous, electrolyte-supported divided electrochemical cell that includes an anode, e.g., an inert metal counterelectrode, in one cell compartment and a metal or p-type semiconductor working cathode electrode in another cell compartment that contains a catalyst of one or more substituted or unsubstituted aromatic heterocyclic amines to produce a reduced organic product. CO₂ is continuously bubbled through the cathode electrolyte solution to saturate the solution.

For electrochemical reduction, the electrode may be chosen from any suitable metal electrode, such as Au, Ag, Zn, Pd, Ga, Hg, In, Cd, Ti and Pt. Pt and hydrogenated Pd have been found to be especially suitable. For photoelectrochemical reduction, the electrode may suitably be chosen from p-type semiconductors such as p-GaAs, p-GaP, p-InN, p-InP, p-CdTe, p-GainP₂ and p-Si.

The catalyst for conversion of carbon dioxide electrochemically or photoelectrochemically may be selected from any substituted or unsubstituted aromatic heterocyclic amine. Suitable amines are heterocycles which are 5- or 6-member rings with at least one ring nitrogen. For example, pyridine, imidazole and their substituted derivatives have been found to be especially suitable as catalysts for either the electrochemical reduction or the photoelectrochemical reduction. It is also envisioned the other aromatic amine, e.g., quinolines, are also effective electrocatalyts.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention may be better understood and appreciated by reference to the detailed description of specific embodiments presented herein in conjunction with the accompanying drawings of which:

FIG. 1 is a flow chart for the electrochemical reduction of in accordance with embodiments of the invention; and

FIG. 2 is a flow chart for the photoelectrochemical reduction of CO₂ in accordance with embodiments of the invention.

DETAILED DESCRIPTION

Embodiments of the present invention relate to the simple, efficient, and economical conversion of carbon dioxide to reduced organic products, such as methanol, formic acid and formaldehyde.

It has been previously known that carbon dioxide can be photochemically or electrochemically reduced to formic acid with formaldehyde and methanol being formed in only smaller amounts. Catalytic hydrogenation of carbon dioxide using heterogeneous catalysts is also known to provide methanol together with water as well as formic acid and formaldehyde. Also known is the reduction of carbon dioxide to methanol with complex metal hydrides, such as lithium aluminum hydride, a process which is extremely costly, and therefore, not suited for the bulk production of methanol. Such known current processes are highly energy-consuming, and are not efficient ways for a high yield, economical conversion of carbon dioxide to organic products, e.g., methanol.

On the other hand, the use of processes for converting carbon dioxide to reduced organic products in accordance with embodiments of the invention has the potential to lead to a significant reduction of carbon dioxide, a major greenhouse gas, in the atmosphere, thus to mitigation of global warming. Moreover, the present invention advantageously produces methanol and related products without the need of adding extra reactants, such as a hydrogen source. The resultant product mixture requires little in the way of further treatment. For example, a resultant 1 M methanol solution may be used directly in a fuel cell. For other uses, simple removal of the electrolyte salt and water are readily accomplished.

Before any embodiments of the invention are explained in detail, it is to be understood that the invention is not limited in its application of the details of the structure or the function of the invention set forth in the following description or illustrated in the appended figures of the drawing. The invention is capable of other embodiments and of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of terms such as “including,” “comprising,” or “having” and variations thereof herein is meant to encompass the item listed thereafter and equivalents thereof as well as additional items. Further, unless otherwise noted, technical terms are used according to conventional usage.

Further, unless otherwise noted, technical terms are used according to conventional usage. Definitions of standard chemistry terms may be found in reference works, such as Carey and Sundberg “ADVANCED ORGANIC CHEMISTRY 4^(th) ED.” Vols. A (2000) and B (2001), Plenum Press, New York. Unless otherwise indicated, conventional methods of mass spectroscopy, NMR, spectrophotometry, and gas chromatography, within the skill of the art are employed. The nomenclature employed in connection with, and the laboratory procedures and techniques of, electrochemistry, analytical chemistry, and synthetic organic chemistry described herein are generally those known in the art. However, as used herein, the following definitions may he useful in aiding the skilled practitioner in understanding the invention.

An “alkyl group refers to an aliphatic hydrocarbon group. The alkyl moiety may be a “saturated alkyl” group (i.e., no alkene or alkyne moieties), or an “unsaturated alkyl” moiety, which means that it contains at least one alkene or alkyne moiety. The alkyl moiety, whether saturated or unsaturated, may be branched, straight chain, or cyclic. Depending on the structure, an alkyl group can be a monoradical or a diradical (i.e., an alkylene group). As used herein, is the designation C₁-C_(x), which includes C₁-C₂, C₁-C₃, C₁-C₄ . . . C₁-C₁₀ . . . C₁-C_(x).

The “alkyl” moiety may have 1 to 30 carbon atoms (whenever it appears herein, a numerical range such as “1 to 30” refers to each integer in the given range; e.g., “1 to 30 carbon atoms” means that the alkyl group may have 1 carbon atom, 2 carbon atoms. 3 carbon atoms, etc., up to and including 30 carbon atoms, although the present definition also covers the occurrence of the term “alkyl” where no numerical range is designated). A “lower alkyl” moiety may have 1 to 10 carbons. For example, the lower alkyl group of the compounds described herein may be designated as “C₁-C₁₀ alkyl” or similar designations. By way of example only, “C₁-C₁₀ alkyl” includes C₁-C₂ alkyl, C₁-C₃ alkyl, C₁-C₄ . . . C₁-C₁₀ alkyl. Typical lower alkyl groups include, but are in no way limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, and decyl. Lower alkyl groups can be substituted or unsubstituted.

The term “aromatic’ refers to a planar ring having a delocalized π-electron system containing 41n+2 π-electrons, where n is an integer. Aromatic rings can be formed by five, six, seven, eight, nine, or more than nine atoms. Aromatics can be optionally substituted. The term “aromatic” includes both carbocyclic aryl (e,g., phenyl) and heterocyclic aryl (or “heteroaryl” or “heteroaromatic”) groups (e.g., pyridine). The term also includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of carbon atoms) groups.

As used herein, the term “aryl” refers to an aromatic ring wherein each of the atoms forming the ring is a carbon atom. Aryl rings can be formed by five, six, seven, eight, nine, or more than nine carbon atoms. Aryl groups can he optionally substituted. Examples of aryl groups include, but are not limited to phenyl, naphthalenyl, phenanthrenyl, anthracenyl, fluorenyl, and indenyl. Depending on the structure, an aryl group can be a monoradical or a diradical (i.e., an arylene group).

As used herein, the term “ring” refers to any covalently closed structure. Rings include, for example, carbocycles (e.g., aryls and cycloalkyls), heterocycles (e.g., heteroaryls and non-aromatic heterocycles), aromatics (e.g. aryls and heteroaryls), and non-aromatics (e.g., cycloalkyls and non-aromatic heterocycles). Rings can be optionally substituted. Rings can also form part of a ring system.

As used herein, the term “ring system” refers to two or more rings, wherein two or more of the rings are fused. The term “fused” refers to structures in which two or more rings share one or more bonds.

The terms “heteroaryl,” “heteroaromatic” or “aromatic hetercyclic” refers to an aryl group that includes one or more ring heteroatoms selected from nitrogen, oxygen and sulfur. An N-containing “heteroaromatic” or ‘heteroaryl’ moiety refers to an aromatic group in which at least one of the skeletal atoms of the ring is a nitrogen atom. The polycyclic heteroaryl group may be fused or non-fused. Illustrative examples of N-containing aromatic heterocyclic groups include the following moieties:

and the like. Depending on the structure, a heteroaryl group can be a monoradical or a diradical (i.e., a heteroarylene group).

The term “membered ring” can embrace any cyclic structure. The term “membered” is meant to denote the number of skeletal atoms that constitute the ring. Thus, for example, cyclohexyl, pyridine, and pyran are 6-membered rings and cyclopentyl and pyrrole, are 5-membered rings.

The term “moiety” refers to a specific segment or functional group of a molecule. Chemical moieties are often recognized chemical entities embedded in or appended to a molecule.

As used herein, the substituent “R” appearing by itself and without a number designation refers to a optional substituent as defined in certain formulas herein.

In the following description of methods in accordance with embodiments of the invention, process steps are carried out at temperatures of 10° C. to 50° C. and pressures of 1 to 10 atmospheres unless otherwise specified. It also is specifically understood that any numerical range recited herein includes all values from the lower value to the upper value, e.g., all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in the application. For example, if a concentration range or beneficial effect range is stated as 1% to 50%, it is intended that values such as 2% to 40%, 10% to 30%, or 1% to 3%, etc., are expressly enumerated in this specification. These are only examples of what is specifically intended.

Further, no admission is made that any reference, including any patent or patent document, citied in this specification constitutes prior art. In particular, it will be understood that unless otherwise stated, reference to any document herein does not constitute an admission that any of these documents forms part of the common general knowledge in the art in the United States or in any other country. Any discussion of the references states what their authors assert, and applicant reserves the right to challenge the accuracy and pertinence of any of the documents cited herein.

It has now been found that the use of electrochemical or photoelectrochemical reduction of carbon dioxide (CO₂), tailored with certain electrocatalysts, produces methanol and related products in a high yield of about 60 to about 100%, based on the amount of CO₂, suitably about 75 to 90%, and more suitably about 85 to 95%. At an electric potential of about −0.09 to −0.5 V with respect to a standard calomel electrode (SCE), methanol can be produced with good faradaic efficiency at the cathode,

The overall ea ion for the reduction of CO₂ is represented as:

CO₂+2 H₂O→CH₃OH+3/2O₂

For the 6 e− reduction, the reactions at the cathode and anode are:

CO₂+6H⁺ 6 e⁻→CH₃OH+H₂O (cathode)

3 H₂O→3/2 O₂+6 H⁺+6 e⁻ (anode)

FIGS. 1 and 2 illustrate the general method in accordance with embodiments of the invention for catalyzed electrochemical and photoelectrochemical conversion of CO₂ to reduced organic products. The reduction of CO₂ is suitably achieved in an efficient manner in a divided electrochemical or photoelectrochemical cell in which a first compartment contains an anode which is an inert counterelectrode, and a second compartment containing a working cathode electrode and one or more substituted or unsubstituted aromatic heterocyclic amines. The compartments are separated by a porous glass frit or other ion conducting bridge. Both compartments contain an aqueous solution of an electrolyte such as KCl. CO₂ is continuously bubbled through the cathodic electrolyte solution to saturate the solution,

In the working electrode compartment, carbon dioxide is continuously bubbled through the solution. In one embodiment, if the working electrode is a metal, then an external bias is impressed across the cell such that the potential of the working electrode is held constant, e.g., between −0.5 V to −0.9 V v. SCE. In another embodiment, if the working electrode is a p-type semiconductor, the electrode is suitably illuminated with light of energy equal to or greater than the bandgap of the semiconductor during the electrolysis, and either no external source of electrical energy is required or a modest bias of about 500 mV is applied. The working electrode potential is held constant, e.g. between −0.5 to +0.2 V v. SCE. The electrical energy for the electrochemical reduction of carbon dioxide can come from a conventional energy source, including nuclear and alternatives (hydroelectric, wind, solar power, geothermal, etc.), from a solar cell or other non-fossil fuel source of electricity, provided that the electrical source supply at least 1.6 V across the cell, although this minimum value may be adjusted depending on the internal resistance of the cell employed.

Advantageously, the carbon dioxide used in the embodiments of the invention can be obtained from any sources, e.g., an exhaust stream from fossil-fuel burning power or industrial plants, from geothermal or natural gas wells or the atmosphere itself. Most suitably, however, carbon dioxide is obtained from concentrated point sources of its generation prior to its release into the atmosphere. For example, high concentration carbon dioxide sources are those frequently accompanying natural gas in amounts of 5 to 50%, those from flue gases of fossil fuel (coal, natural gas, oil, etc.) burning power plants, and nearly pure CO₂ exhaust of cement factories and from fermenters used for industrial fermentation of ethanol. Certain geothermal steams also contains significant amounts of CO₂. In other words, CO₂ emissions from varied industries, including geothemial wells, can be captured on-site. Separation of CO₂ from such exhausts is well-developed. Thus, the capture and use of existing atmospheric CO₂ in accordance with embodiments of the invention allows CO₂ to be a renewable and unlimited source of carbon.

For electrochemical conversion. CO₂ is readily reduced in the aqueous medium with a metal electrode, such as a Pt and hydrogenated Pd electrode, although other metal electrodes. e.g., Au, Ag, Zn, Ga, Hg, In, Cd and Ti may also be effective. Faradaic efficiencies have been found to be high, reaching about 100%.

For photoelectrochemical conversion, CO₂ is readily reduced with a p-type semiconductor electrode, such as p-GaP, p-GaAs, p-InP, p-InN, p-WSe₂, p-CdTe, p-GaInP₂ and p-Si.

In embodiments of the invention, the electrochemical/photoelectrochemical reduction of CO₂ utilizes one or more substituted or unsubstituted aromatic heterocyclic amines as homogeneous catalysts in aqueous solution. Aromatic heterocyclic amines include, for example, unsubstituted and substituted pyridines, pyroles, imidazoles and benzimidazoles. Substituted pyridines and imidazoles may include mono- and disubstituted pyridines and imidazoles. For example, suitable catalysts may include straight chain or branched chain lower alkyl (e.g., C₁-C₁₀) mono- and disubstituted compounds such as 2-methylpyridine, 4-tertbutyl pyridine, 2,6-dimethylpyridine (2,6-lutidine); hipyridines, such as 4,4′-bipyridine; amino-substituted pyridines, such as 4-dimethylamino pyridine and hydroxyl-substituted pyridines, e.g., 4-hydroxy-pyridine, and substituted or unsubstituted quinoline or isoquinolines. Catalysts may also suitably include substituted or unsubstituted dinitrogen heterocyclic amines such a pyrazine, pyridazine and pyrimidine.

In some embodiments, the aromatic heterocyclic amine catalysts may be represented by formula

wherein the ring structure W is an aromatic 5- or 6-member heterocylic ring with at least one ring nitrogen and is optionally substituted at one or more ring positions other than nitrogen with R, and

wherein L is C or N, R¹ is H, R² is H if L is N or R² is R if L is C, and R is an optional substituent on any ring carbon and is independently selected from H, straight chain or branched chain lower alkyl, hydroxyl, amino, pyridyl, or two R's taken together with the ring carbons to which they are bonded are a fused six-member aryl ring, and n=0 to 4.

In some embodiments, the substituted or unsubstituted aromatic 5- or 6-member heterocyclic amines may be represented by the following formulas (2), (3) or (4) For example, a catalyst in accordance with embodiments of the invention which is a 6-member heterocycline ring having one nitrogen in the ring is represented by formula (2):

wherein R³ is H; R⁴, R⁵, R⁷ and R⁸ are independently H, straight chain or branched chain lower alkyl, hydroxyl, amino, or taken together with the ring carbons to which they are bonded are a fused six-member aryl ring, and R⁵ is H, straight chain or branched chain lower alkyl, hydroxyl, amino or pyridyl.

A catalyst in accordance with embodiments of the invention which is a 6-member heterocyclic amine having two nitrogen in the ring is represented by formula (3):

wherein one of L¹, L² and L³ is N, while the other L's are C, R⁹ is H, if L¹ is N, then R¹⁰ is H, if L² is N, then R¹¹ is H, and if L³ is N, then R¹² is H; and if L¹, L² or L³ is C, then R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ are independently selected from straight chain or branched chain lower alkyl, hydroxyl, amino, or pyridyl.

A catalyst in accordance with embodiments of the invention which is a 5-member heterocyclic amine having one or two nitrogen in the ring is represented by formula (4):

wherein L⁵ is N or C, R¹⁵ is H, R¹⁶ is H if L⁵ is N, or if is C, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ are independently selected from straight chain or branched chain lower alkyl, hydroxyl, amino, or pyridyl, or R¹⁷ and R¹⁸ taken together with the ring carbons to which they are bonded are a fused six-member aryl ring.

Suitably, the concentration of aromatic heterocyclic amine catalysts is about 1-mM to 1 M. The electrolyte is suitably a salt, such as KCl or NaNO₃, at a concentration of about 0.5M. The pH of the solution is maintained at about pH 3-6, suitably about 4.7- 5.6.

At metal electrodes, formic acid and formaldehyde were found to be intermediate products along the pathway to the 6 e⁻ reduced product of methanol, with an aromatic amine radical, e.g. the pyridinium radical, playing a role in the reduction of both intermediate products. It has been found, however, that these intermediate products can also be the final products of the reduction of CO₂ at metal or p-type semiconductor electrodes, depending on the particular catalyst used. Other C—C couple products are also possible. For example, reduction of CO₂ can suitably yield formaldehyde, formic acid, glyoxal, methanol, isopropanol, or ethanol, depending on the particular aromatic heterocyclic amine used as the catalyst. In other words, in accordance with the invention, the products of the reduction of CO₂ are substitution-sensitive. As such, the products can be selectively produced. For example, use of 4,4′-bipyridine as the catalyst can produce methanol and/or 2-propanol; lutidines and amino-substituted pyridines can produce 2-propanol; hydroxy-pyridine can produce formic acid; imidazoles can produce methanol or formic acid depending on conditions.

The effective electrochemical/photoelectrochemical reduction of carbon dioxide disclosed herein provides new methods of producing methanol and other related products in an improved, efficient, and environmentally beneficial way, while mitigating CO₂-caused climate change (e.g. global warming).

Moreover, the methanol product of reduction of carbon dioxide can be advantageously used as (1) a convenient energy storage medium, which allows convenient and safe storage and handling; (2) a readily transported and dispensed fuel, including for methanol fuel cells; and (3) a feedstock for synthetic hydrocarbons and theft products currently obtained from oil and gas resources, including polymers, biopolymers and even proteins, which can be used for animal feed or human consumption. Importantly, the use of methanol as an energy storage and transportation material eliminates many difficulties of using hydrogen for such purposes. The safety and versatility of methanol makes the disclosed reduction of carbon dioxide further desirable.

EXAMPLES

Embodiments of the invention are further explained by the following examples, which should not be construed by way of limiting the scope of the invention.

Example 1 General Electrochemical Methods

Chemicals and materials. All chemicals used were >98% purity and used as received from the vendor (e.g., Aldrich), without further purification. Either deionized or high purity water (Nanopure, Barnstead) was used to prepare the aqueous electrolyte solutions.

Electrochemical system. The electrochemical system was composed of a standard two-compartment electrolysis cell to separate the anode and cathode reactions. The compartments were separated by a porous glass frit or other ion conducting bridge. 0.5 M KCl (EMD >99%) was used as the supporting electrolyte. A concentration of the desired aromatic heterocyclic amine, such as pyridine, pyridine derivative, imidazole, imidazole derivative, of between about 1 mM to 1M was used.

The working electrode consisted of a known area Pt foil connected to a Pt wire (both Aldrich) or a Pd foil (Johnson Matthey), Pd electrodes were hydrogenated at a current density of 15 mA cm⁻² in 1 M H₂SO₄ until ˜73 C were passed. All potentials were measured with respect to a saturated calomel reference electrode (SCE) (Accumet). The three-electrode assembly was completed with a Pt mesh electrode also connected to a Pt wire. Before and during all electrolyses, CO₂ (Airgas) was continuously bubbled through the electrolyte to saturate the solution. The resulting pH of the solution was maintained at about pH 3 to pH 6, suitably, pH 4.7 to pH 5.6, depending on the aromatic heterocyclic amine employed. For example, under constant CO₂ bubbling, the pH's of 10 mM solutions of 4-hydroxy pyridine, pyridine, and 4-tertbutyl pyridine were 4.7, 5.28 and 5.55, respectively. For NMR experiments, isotopically enriched ¹⁵N pyridine (>98%) and ¹³C NaHCO₃ (99%) were obtained from Cambridge Isotope Laboratories, Inc.

Example 2 General Photoelectrochemical Methods

Chemicals and materials. All chemicals used in this work were analytical grade or higher. Either deionized or high purity water (Nanopure, Barnstead) was used to prepare aqueous electrolyte solutions,

Photoelectrochemical system. The photoelectrochemical system was composed of a Pyrex three-necked flask containing 0.5 M KCl as supporting electrolyte and a 1 mM-1M catalyst, e.g., 10 mM pyridine or pyridine derivative. The photocathode was a single crystal p-type semiconductor, which was etched for ˜1-2 min in a bath of concentrated HNO3:HCl, 2:1 v/v prior to use. An ohmic contact was made to the hack of the freshly etched crystal using an indium/zinc (2 wt. % Zn) solder. It was then connected to an external lead with conducting silver epoxy (Epoxy Technology H31), that was covered in glass tubing, and insulated using an epoxy cement (Loctite 0151 Hysol) to expose only the front face of the semiconductor to solution. All potentials were referenced against a saturated calomel electrode (Accurnet). The three-electrode assembly was completed with a carbon rod counter electrode to minimize the re-oxidation of reduced CO₂ products. During all electrolyses, CO₂ (Airgas) was continuously bubbled through the electrolyte to saturate the solution. The resulting pH of the solution was maintained at about pH 3-pH 6, e.g., pH 5,2.

Light sources. Four different light sources were used for the illumination of the p-type semiconductor electrode. For initial electrolysis experiments, a Hg—Xe arc lamp (USHIO UXM 200H) was used in a lamp housing (PTI Model A-1010) and powered by a PTI LTS-200 power supply. Similarly, a Xe arc lamp (USHIO UXL 151H) was used in the same housing in conjunction with a PTI monochromator to illuminate electrode at various specific wavelengths. A fiber optic spectrometer (Ocean Optics S2000) or silicon photodetector (Newport 818-SL silicon detector) was used to measure the relative resulting power emitted through the monochromator. The flatband potential was obtained by measurements of the open circuit photovoltage during various irradiation intensities using the 200 W Hg—Xe lamp (3 W!cm2-23 W/cm2). The photovoltage was observed to saturate at intensities above ˜6 W/cm2. For quantum yield determinations, electrolyses were performed under illumination by two different light emitting diodes (LEDs). A blue LED (Luxeon V Dental Blue, Future Electronics) with a luminous output of 500 mW+/−50 mW at 465 nm and a 20 nm fwhm was driven at its maximum rated current of 700 mA using a Xitanium Driver (Advance Transformer Company). A Fraen collimating lens (Future Electronics) was used to direct the output light. The resultant power density that reached the window of the photoelectrochemical cell was determined to be 42 mW/cm2, measured using a Scientech 364 thermopile power meter and silicon photodector. It was assumed that the measured power density is greater than the actual power density observed at the semiconductor face since there is luminous intensity loss through the solution layer between the wall of the photoelectrochemical cell and the electrode.

Example 3 Analysis of Products of Electrolysis

Electrochemical experiments were performed using a PAR 173 patentiostat-galvanostat together with a PAR 379 digital coulometer, a PAR 273 potentiostat-galvanostat, or a DLK-60 electrochemical analyzer. Electrolyses were run under potentiostatic conditions from ˜6-30 hrs until a relatively similar amount of charge was passed for each run.

Gas Chromatography. The electrolysis samples were analyzed using a gas chromatograph (HP 5890 GC) equipped with an FID detector. Removal of the supporting electrolyte salt was first achieved with Amberlite IRN-150 ion exchange resin (cleaned prior to use to ensure no organic artifacts by stirring in a 0.1% v/v aqueous solution of Triton X-100, reduced (Aldrich), filtered and rinsed with a copious amount of water, and vacuum dried below the maximum temperature of the resin (−60° C.) before the sample was directly injected into the GC which housed a DB-Wax column (Agilent Technologies, 60 m, 1 μm film thickness.) Approximately 1 g of resin was used to remove the salt from 1 mL of sample. The injector temperature was held at 200° C. the oven temperature maintained at 120° C. and the detector temperature at 200° C. During a typical run, only peaks related to the elution of methanol and pyridine were observed.

Spectrophotometry; The presence of formaldehyde and formic acid was also determined by the chromotropic acid assay. Briefly, a solution of 0.3 g of 4,5-dihydroxynaphthalene-2,7-disulfonic acid, disodium salt dihydrate (Aldrich) was dissolved in 10 mL deionized water before diluting to 100 mL with concentrated sulfuric acid. For formaldehyde, an aliquot of 1.5 mL was then added to 0.5 mL of sample. The presence of formaldehyde (absorbance at 577 nm) was detected against a standard curve using an HP 8453 UV-Vis spectrometer. For formic acid, a 0.5 mL aliquot of sample was first reduced with a ˜100 mg piece of Mg wire and 0.5 mL concentrated hydrochloric acid (added slowly in aliquots over a 10 min period) to convert to formaldehyde before following the chromotropic acid assay as described above.

Mass spectrometry. Mass spectral data was also collected to identify all organics. In a typical experiment, the sample was directly leaked into an ultrahigh vacuum chamber and analyzed by an attached SRS Residual Gas Analyzer (with the ionizer operating at 70 eV and an emission current of 1 mA). Samples were analyzed against standard methanol spectra obtained at the same settings to ensure comparable fragmentation patterns. Mass spectral data confirmed the presence of methanol and also proved that the initial solution before electrolysis contained no reduced CO₂ species. Control experiments also showed that after over 24 hours under illumination the epoxy used to insulate the backside of the electrode did not leach any organic material that would give false results for the reduction of CO₂ ¹⁷NMR spectra of electrolyte volumes after illumination were obtained using an automated Balker Ultrashieki™ 500 Plus spectrometer with an excitation sculpting pulse technique for water suppression. Data processing was achieved using MestReNova software. For methanol standards and electrolyte samples, the representative signal for methanol was observed between 3.18-3.30 ppm.

NMR. NMR spectra of electrolyte volumes after bulk electrolyses were also obtained using an automated Bruker Ultrashield™ 500 Plus spectrometer with an excitation sculpting pulse technique for water suppression. Data processing was achieved using MestReNova software. The concentrations of formate and methanol present after bulk electrolyses were determined using acetone as the internal standard. For ¹⁵N—¹³C coupling experiments, ¹³C NMR spectra were obtained using an automated Bruker Ultrashield™ 500 Plus spectrometer tuned for maximum ¹³C sensitivity. In a typical experiment, an aqueous solution containing 10% deuterium oxide (Cambridge Isotope Laboratories, Inc., >99.9%), 0.5M KCl, 50 mM of ¹⁵N pyridine, and 33 mM of ¹³C NaHCO₃ was first purged with Ar in a septa sealed NMR tube; then pH was adjusted using 1 M H₂SO₄ to a pH of 5.2. At this pH, the bicarbonate was observed to be completely in the dissolved ¹³CO₂ form. No peak associated with HCO₃ was seen. The temperature of the experiment was maintained at 295° K, however, the temperature of the instrument was also adjusted to access the temperature dependence on the ¹⁵N—¹³C coupling. The sample tube was held for at least 10 minutes at the given temperature before the spectra were obtained to ensure temperature equilibrium. A temperature range of 275° K. to 306° K. was examined.

Example 4 Electrolysis with Monosubstituted Pyridines

Electrolyses were performed for various monosubstituted pyridines. These electrocatalysts were present at a concentration of 10 mM in 50 mL of water and 0.5 M KCl (as the supporting electrolyte). The cathode was either Pt or hydrogenated Pd, galavanostatically held at 50 μA cm⁻², and saturated with CO₂. Products of the electrolyses were analyzed as described above in Example 3. The results, which are the averages of at least three experiments, are given in Table 1 below.

TABLE 1 Results for bulk electrolyses for monoalkyl or amino-substituted pyridine electrocatalysts Faradaic Yield (%) Electrocatalyst HCOOH^(a) CH₃OH Total Yield^(e) pyridinium 10.8 ± 0.5 22 ± 2 33 ± 3 2-methyl 16 ± 4 26 ± 4 42 ± 8 pyridinium 4-methyl  7 ± 3 31 ± 3 38 ± 6 pyridinium 4-tertbutyl trace 14.5 ± 2  14.5 ± 2  pyridinium 4-amino 12 ± 4 39 ± 4 51 ± 8 pyridinium 4-dimethyl  7 ± 2 11 ± 1 18 ± 3 amino pyridinium 4-hydroxy 12 ± 1 15 ± 3 27 ± 4 pyridinum ^(a)Mostly in the formate form at the pH's of the solutions used; ^(e)Total faradaic yield for observed CO₂-derived products, not including competing hydrogen generation.

Example 5 Electrolysis of Dialkylsubstituted Pyridines (Lutidines)

Electrolyses were performed for various disubstituted pyridines or lutidines. These electrocatalysts were present at a concentration of 10 mM in 50 mL of water and 0.5 M KCl (as the supporting electrolyte). The cathode was either Pt or hydrogenated Pd. galavanostatically held at 50 μA cm², and saturated with CO₂. Products of the electrolyses were analyzed a described above in Example 3. The results, which are the averages of at least three experiments, are given in Table 2 below.

TABLE 2 Results for bulk electrolyses for various lutidine electrocatalysts Faradaic efficiency η, % Electrocatalyst Acetaldehyde Acetone Methanol 2-propanol Ethanol 3,5-lutidinium trace trace-5.9 3.2-8.0  trace-9.5 trace-5.3 3,4-lutidinium trace trace-5.6 4.4-9.2 trace-12 trace-3.0 2,3-lutidinium trace trace-9.4 5.9-8.4 trace-12 trace-3.4 2,4-lutidinium trace trace-8.6 4.5-13  trace-16 trace-5.4 2.6-lutidinium trace   2.9-5.8 3.6-8.2 trace-14 trace-6.3

Example 6 Electrolysis of 4,4′-bipyridine

Electrolysis was carried out in aqueous solution containing 10 mM 4,4′-bipyridine with 0.5 M KCl as the supporting electrolyte. The pH was maintained at a constant 5.22, under CO₂ saturation. The results represent the average of at least three independent experiments, and are given below in Table 3.

TABLE 3 Electrolysis of 4,4′-bipyridine Faradaic efficiency η, % E (V)a Acetaldehyde Acetone Methanol 2-Propanol Ethanol −0.725 trace 3 ± 1 53 ± 13  4 ± 2 trace −1.1 trace 7 ± 4 20 ± 2  20 ± 8 trace

Example 7 Photoelectrolysis of Iutidines and Bipyridine

Photoelectrolysis was carried out in aqueous solution containing 10 mM lutidine or bypyridine electrocatalyst in 50 mL water with 0.5 M KCl as the supporting electrolyte. The pH was maintained at a constant 4.7, under CO₂ saturation. The photoelectrochemical cell was a p-GaP, p-GaInP2, or p-Si photoelectrode. For the p-GaP system, the wavelength of 365 nm was chosen to correspond to the lowest energy direct bandgap of 2.8 eV. With an indirect bandgap of 2.24 eV, p-GaP can only absorb ˜17% of solar radiation. Therefore, both a p-GainP2 photocathode, with a direct bandgap of 1.81 eV, and p-Si, with an indirect bandgap of 1.12 eV, were examined as potential photoelectrodes to increase the percentage of solar radiation that can be converted into stored chemical energy. The commercially available wavelengths of 465 nm and 530 nm were examined for illumination of the p-GaInP₂ cell and the p-Si cell, respectively. However, wavelengths as long as ˜685 nm and ˜1100 nm can he used to excite p-GaInP₂ and p-Si, respectively.

At a pH of 5.22 for the 4,4′-bipyridine system, the thermodynamic potential for the reduction of CO₂ to methanol is approximately −0.52 V vs. SCE. At the pH of 5.55 for the lutidine-based system, this potential is ˜0.54 V vs. SCE. Similarly, the thermodynamic reduction potential of CO₂ to 2-propanol at the pH's of 5.22 and 5.55 is −0.52 V vs. SCE and −0.54 V vs. SCE, respectively. The results of bulk electrolysis given as faradaic efficiencies are reported below in Table 4.

TABLE 4.4 Faradaic efficiencies and quantum yields for the reduction of CO₂ to various products. Faradaic Efficiency η, (%) E(V) vs. j(μA/ 2- Cat. SCE cm²) Acetal Acetone MeOH PrOH EtOH p-GalnP₂ 4,4′ −0.5 241 Trace trace 5.5 1.5 — 465 nm 4,4′ −0.4 181 Trace trace 8.2 2.8 — 4,4′ −0.3 70 Trace trace 29 22 — 3,5 lut^(a) −0.5 146 Trace 5.9 7.2 3.7 — 2,3 lut −0.5 8.1 Trace trace 9.2 5.3 — 2,4 lut −0.5 161 Trace trace 21 8.3 — 2,6 lut −0.5 14 Trace trace 51 21 — p-GaP 3.5 lut −0.5 10 Trace 2.9 51 trace — 365 nm 3,4 lut −0.5 13 Trace trace 63 15 — 2,3 lut −0.5 42 Trace trace 48 28 — 2,4 lut −0.5 32 Trace trace 21 29 — 2.6 lut −0.5 9.5 Trace trace 38 63 — 4,4′ −0.4 70 Trace trace 11 5 — p-Si 4,4′ −0.6 41.5 Trace trace 18 24 — 530 nm ^(a)“lut” is a an abbreviation for lutidine; 4,4′ is an abbreviation for 4,4′-bipyridine.

Enhanced yields were observed for the lutidinium catalysts and high yields for 4,4′-bipyridinium. In some instances, nearly 100% faradaic yields were observed for CO₂-derived products. The yields for 2-propanol represent the highest reported 2-propanol yields known to the inventors with 2,6-lutidine in a p-GaP photoelectrochemical system yielding as high as 63% faradaic efficiency for 2-propanol. The data reported in Table 4 for methanol and 2-propanol, at −0.5 V vs. SCE and potentials less negative, was observed at essentially zero overpotential, that is, at a potential approaching the short circuit potential for the iR compensated cell. This corresponds to the conversion of light energy into storable chemical energy in the form of highly reduced CO₂ products. To the inventors' best knowledge, this is the first report of the reduction of CO₂ to 2-propanol using only energy.

Example 9 Electrolysis/Photoelectrolysis of Imidazoles

Electrolyses are performed for various imidazoles, including benzimidazoles. These electrocatalysts are present at a concentration of 10 mM in 50 mL of water and 0.5 M KCl (as the supporting electrolyte). The cathode is Pt or illuminated P-GaP, galavanostatically held at 50 μA cm⁻², and saturated with CO₂. Products of the electrolyses are analyzed as described above in Example 3.

Example 10 Electrolysis/Photoelectrolysis at Varying Temperatures and Pressures

Electrolyses are carried out at various temperatures and pressures to determine their effect on the products and yield. Electrolyses are carried out at temperatures from 10° C. to 50° C. The results demonstrate that the kinetics of the electrolysis reaction are increased with increased temperature, with peak currents following the Arrhenius rate law with an observed activation barrier of 10-15 kJ/mole, although the solubility of the CO₂ is decreased with increased temperature.

Electrolyses are carried out at pressure from 1 atmosphere to 10 atmospheres. The results demonstrate that product yields can be increased with increased pressure due to the increased solubility of CO₂ at higher pressures. For example, pressure data at 5 atm indicates a 3.5 increase in current compared to 1 atm.

Temperature and pressure can be optimized to produce efficient and higher product yields.

In summary, embodiments of the invention provide that carbon dioxide can be efficiently converted to value added products, using either a minimum of electricity (that could be generated from an alternate energy source) or directly using visible light. The processes of the embodiments of the invention generate high energy density fuels that are not fossil-based as well as being chemical feedstocks that are not fossil or biologically based. Moreover, the catalysts for these processes are substituents-sensitive, and provide for selectivity of the value added products.

The foregoing description is considered as illustrative only of the principles manifest in embodiments of the invention. Numerous modifications and changes may readily occur to those skilled in the art, and it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents are considered to fall within the scope of the invention. Various features and advantages of the invention are set forth in the appended claims and their equivalents. It is intended that the scope of the present invention be limited solely by the broadest interpretation that lawfully can he accorded the appended claims.

All publications, patents and patent applications referenced in this specification are indicative of the level of ordinary skill in the art to which this invention pertains. All publications, patents and patent applications are herein expressly incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated by reference. In case of conflict between the present disclosure and the incorporated patents, publications and references, the present disclosure should control.

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1-28. (canceled)
 29. An environmentally beneficial method of producing methanol by electrochemical or photoelectrochemical reduction of any available source of carbon dioxide, which comprises: providing a divided electrochemical cell comprising an anode in a first cell compartment and a cathode electrode in a second cell compartment that also contains a catalyst which is one or more of a substituted or unsubstituted aromatic heterocyclic amine, both compartments containing an aqueous solution of an electrolyte, providing carbon dioxide from an existing source into the second cell compartment; electrochemically or photoelectrochemically reducing the carbon dioxide in the second cell compartment to produce methanol to reduce atmospheric carbon dioxide. 